WO2012072639A1 - Appareil et procédé pour la polymérisation d'oléfines - Google Patents

Appareil et procédé pour la polymérisation d'oléfines Download PDF

Info

Publication number
WO2012072639A1
WO2012072639A1 PCT/EP2011/071299 EP2011071299W WO2012072639A1 WO 2012072639 A1 WO2012072639 A1 WO 2012072639A1 EP 2011071299 W EP2011071299 W EP 2011071299W WO 2012072639 A1 WO2012072639 A1 WO 2012072639A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction zone
reaction
inlet
gas
separation unit
Prior art date
Application number
PCT/EP2011/071299
Other languages
English (en)
Inventor
Andrew David Bell
Kevin Peter Ramsay
Original Assignee
Ineos Commercial Services Uk Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ineos Commercial Services Uk Limited filed Critical Ineos Commercial Services Uk Limited
Priority to CN201180057160.4A priority Critical patent/CN103221124B/zh
Priority to EP11788493.2A priority patent/EP2646139B1/fr
Priority to US13/885,574 priority patent/US8765885B2/en
Publication of WO2012072639A1 publication Critical patent/WO2012072639A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/0045—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by means of a rotary device in the flow channel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • B01J8/384—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only
    • B01J8/388—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only externally, i.e. the particles leaving the vessel and subsequently re-entering it
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00761—Discharging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00769—Details of feeding or discharging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/92—Apparatus for use in addition polymerization processes

Definitions

  • the present invention relates to an apparatus and process for gas phase
  • GB 1 ,413,613 describes a process for the dry polymerisation of olefins in a fluidised bed reactor.
  • Two possible configurations are described to address the potential problem of small solid particles, known as "fines", being entrained from the reactor with the ascending gas stream.
  • the first of these is the use of what is referred to in GB 1 ,413,613 as a "tranquilisation chamber" which is an area of larger cross-section compared to the reactor and provided above the reactor which acts to reduce the velocity of the fluidising gas, allowing solid particles which might otherwise exit the top of the fluidised bed to fall back to the bed.
  • the second is the use of a cyclone to separate the entrained solids for subsequent return to the reactor.
  • the tranquilisation chamber which may alternatively be, and, in fact, is more generally, referred to as a disengagement zone or velocity reduction zone, has become the commonly used means for reducing entrainment from fluidised bed reactors.
  • a disengagement zone it is common for significant quantities of solids to remain entrained in the fluidising gas exiting the disengagement zone. Such solids may foul components of the line through which the fluidising gas is recycled, which can lead to a requirement for shutdown and cleaning.
  • a cyclone in addition to the disengagement zone to separate entrained solids from the fluidising gas exiting the disengagement zone.
  • US 4,882.400 discloses an apparatus for the gas phase polymerisation of olefins in a fluidised bed reactor comprising a disengagement chamber and a cyclone which acts to separate entrained solids from the fluidising gas exiting the reactor, for recycle to the fluidised bed.
  • US 5,382,638 also discloses an apparatus for the gas phase pol merisation of olefins in a fluidised bed reactor comprising a disengagement chamber and a cyclone which acts to separate entrained solids from the fluidising gas exiting the reactor, for recycle to the fluidised bed.
  • Cyclones are also known for essentially the same purpose for vapour phase polymerisation of propylene in horizontal gas phase reactors, for example as described in US 4640963.
  • reaction e.g. fluidising
  • gas passes through and exits the top of the reaction zone and is passed to a cyclone or other solids separation unit, wherein entrained solids are separated from the gas, usually for return to the reaction zone.
  • the gas exits the reaction zone via a length of vertically orientated pipe at the top of the reaction zone and enters the cyclone, which is itself vertically orientated, at or near the top of the cyclone via a length of horizontally orientated pipe.
  • the simplest connection is obtained by simply connecting the vertically orientated pipe to a length of horizontally orientated pipe which passes the gas directly to the cyclone.
  • a polymerisation process using a cyclone may be advantageously operated by locating the cyclone inlet at a vertical height low er than the vertical height of the outlet for removal of gas from the reaction zone.
  • the present invention provides an apparatus for the gas phase polymerisation of olefins, said apparatus comprising;
  • reaction zone comprising a grid at its base
  • the inlet of the solids separation unit is located at a vertical height lower than the outlet for removal of reaction gas from the reaction zone and such that the angle to the horizontal of a straight line drawn between the inlet of the solids separation unit and the outlet for removal of reaction gas from the reaction zone is greater than 20°.
  • the outlet for removal of the reaction gas from the reaction zone is located at a vertical height higher than the inlet for introduction of the reaction gas to the reaction zone.
  • the reaction gas is passed in an overall upwards direction through the reaction zone.
  • the inlet for introduction of a reaction gas to the reaction zone is most preferably located at or close to the base of the reaction zone.
  • the reaction zone comprises a grid at its base, which effectively defines the base of the reaction zone.
  • the grid acts as the base of the bed of polymer particles and to support the polymer particles when not being maintained in the agitated state, for example if the gas flow through the grid is stopped.
  • the reaction gas is introduced to the reaction zone at the base of the reaction zone, and in particular through the grid i.e. the grid also acts as an "inlet located in the lower half of the reaction zone for introduction of a reaction gas to the reaction zone".
  • the outlet for removal of the reaction gas from the reaction zone is in the upper half of the reaction zone, most preferably at or close to the top of the reaction zone.
  • the reaction zone comprises an expanded upper section which acts as (and is usually referred to as) a disengagement zone, and the outlet for removal of the reaction gas from the reaction zone is located at or close to the top of this.
  • reaction gas may be introduced to the reaction zone through the grid at the base of the reaction zone and a second inlet for introduction of reaction gas to the reaction zone may be located above the grid.
  • the inlet of the solids separation unit is located at a vertical height lower than the outlet for removal of reaction gas from the reaction /one.
  • a (nominal) straight line drawn between the inlet of the solids separation unit and the outlet for removal of reaction gas from the reaction zone makes an angle of greater than 20° to the horizontal with an overall downwards direction compared to the horizontal (as determined in the direction from the outlet for removal of reaction gas from the reaction zone to the inlet of the solids separation unit).
  • the inlet of the solids separation unit is located relative to the outlet for removal of reaction gas from the reaction zone such that the angle to the horizontal of a straight line drawn between the two is greater than 30°, and most preferably greater than 45°.
  • the outlet for removal of reaction gas from the reaction zone may, and in general will, still exit in a vertically orientated direction from the top of the reaction zone, such that reaction gas therein will be travelling upwards and vertically, as long as the overall direction between the outlet for removal of reaction gas from the reaction zone and the inlet of the solids separation unit is downwards as described.
  • the outlet for removal of reaction gas from the reaction zone and the inlet of the solids separation unit will generally be connected by pipework such that the reaction gas flows from one to the other.
  • the pipework directly connects the outlet for removal of reaction gas from the reaction zone to the inlet of the solids separation unit with no other units, such as separation stages, in between.
  • no obstructions, such as valves are provided in the pipework.
  • the pipework will comprise sections of different orientations which are joined together form a continuous path from the outlet for removal of reaction gas from the reaction zone to the inlet of the solids separation unit.
  • This section may be of any orientation below the vertical greater than 0° and up to 90° (90° corresponding to a vertical orientation) and which provides flow in a downwards direction.
  • the angle to the horizontal of such sections is greater than 25". preferably greater than 35°. and most preferably greater than 50°.
  • the pipework may comprise sections of orientation angled between horizontal and vertical or may consist of vertical and horizontal sections connected together (by bends) to provide the overall connection.
  • the length of any sections of the pipework between the outlet for removal of reaction gas from the reaction zone and the inlet of the solids separation unit which provide flow in an upward direction is minimised, for example any such sections in total constituting less than 30% of the total length of pipework between the outlet for removal of reaction gas from the reaction zone and the inlet of the solids separation unit, more preferably less than 15% of the total length.
  • no lengths of said pipework which provide flow in an upward direction are present. This avoids the presence of "low points" in the pipework which assists flow.
  • the length of any horizontal sections of the pipework between the outlet for removal of reaction gas from the reaction zone and the inlet of the solids separation unit is minimised, for example such lengths constituting less than 50% of the total length of pipework between the outlet for removal of reaction gas from the reaction zone and the inlet of the solids separation unit, more preferably less than 25% of the total length.
  • At least 50% of the total length of pipework between the outlet for removal of reaction gas from the reaction zone and the inlet of the solids separation unit comprises sections which provide flow in a downward direction, such as at least 75% of the total length is in a downward direction.
  • the vertical separation of the inlet of the solids separation unit from the inlet for introduction of reaction gas into the reaction zone is less than the vertical separation of the inlet of the solids separation unit from the outlet for remov al of reaction gas from the reaction zone i.e. the inlet of the solids separation unit is located at a height generally corresponding to the lower half of the reaction zone.
  • the reaction zone will generally comprise a bed of polymer particles.
  • the inlet of the solids separation unit is located at a height which is below the designed maximum height of the bed in the reaction zone.
  • bed height may be varied during operation for a particular product, or may be different for different polymer products, so whether a particular height is above or below the bed may depend on the reaction being performed.
  • the physical reactor is of a fixed size and will have been designed to accommodate a maximum height of polymer bed in the reaction zone during reaction, this being the "designed maximum height" as used herein. (An example of the "designed maximum height" is the height H c of a cylindrical fluidised bed reactor described further below. Although the reactor can be operated with a fluidised bed height below this height, and sometimes even above it, the "designed maximum height" is a fixed height.)
  • the reaction zone preferably comprises at least one inlet for introduction of recycled solids to the reaction zone which is fluidly connected to a solids outlet of the solids separation unit.
  • the inlet(s) for introduction of recycled solids to the reaction zone may be located at any point in the reaction zone which enables the recycled solids to be introduced to the reaction zone i.e. above the grid.
  • the apparatus may comprise a compressor to provide sufficient motive force for the introduction regardless of the location of introduction.
  • This compressor would typically be located on a motive gas line taken from the main reaction loop, the compressor being upstream of the solids outlet of the solids separation unit.
  • the inlet(s) for introduction of recycled solids to the reaction zone are located in the lower half of the reaction zone, and most usually located so that in use the recycled solids are reintroduced into the bed of polymer particles.
  • the inlet(s) for introduction of recycled solids to the reaction zone may be located at any suitable height relative to the solids outlet of the solids separation unit. By locating the inlet of the solids separation unit at a vertical height lower than the outlet for removal of reaction gas the overall flow of reaction gas and entrained solids is in a downwards direction.
  • Another advantage of the present invention is that it also allows the solids separation unit to he physically located at a lower height relative to the reaction zone. In a commercial scale reactor this can allow a significant reduction in the size of the support structure required for the solids separation unit.
  • Solids separation units such as cyclones, are sources of vibrations, which vibrations can affect the efficiency of the separation but can also cause vibrations in connected pipework and equipment. They thus require a support structure that prevents or minimises these vibrations.
  • a particular advantage of the "lower" cyclone inlet relative to the reactor is that it becomes more practical to support the cyclone independently of the reactor support structure.
  • the reaction zone of an apparatus for the gas phase polymerisation of olefins requires a significant support structure.
  • vertically orientated fluidised bed reactors can be of significant height (tens of metres) and weight, and require a very significant amount of support, usually in the form of a metal and concrete structure which suiTOunds large parts, if not all, of the reactor.
  • it has made sense to attach the cyclone to the top of this structure rather than have a separate support structure for the cyclone which must also be of the height of the reactor.
  • vibrations from the cyclone cause vibrations to the support around the reactor.
  • an apparatus for the gas phase polymerisation of olefins comprising:
  • reaction zone comprising a grid at its base
  • reaction zone and the solids separation unit are supported by independent support structures.
  • the support structures are generally formed of metal and -' ' or concrete, preferably being a metal framework supported on a concrete base for each of the cyclone and reactor. In the present inv ention the support structures are considered to be independent as long as they are separately attached to a base, even if they share a common base e.g. two separate metal frameworks may be attached to a common concrete base structure.
  • a key feature which can be used to define whether structures are independent is whether vibrations in one can pass directly to the other, or whether such vibrations are contained within the first structure. Such can be readily determined, for example using modelling.
  • the inlet of the solids separation unit is preferably located at a vertical height lower than the outlet for removal of reaction gas from the reaction zone and such that the angle to the horizontal of a straight line drawn between the inlet of the solids separation unit and the outlet for removal of reaction gas from the reaction zone is greater than 20°, as in the first aspect of the invention.
  • the apparatus of the present invention may be used for any polymerisation process in which bed of polymer particles are maintained in an "agitated state" in the reaction zone by the passage of the reaction gas through the reaction zone.
  • agitated state 1 is meant that the polymer particles move under influence of the reaction gas passing through the bed. It is a feature of such beds that they have an expanded volume compared to the bed "at rest” i.e. when no reaction gas or other agitation means is applied.
  • the agitated bed volume is at least 10% greater than the volume of the bed "at rest”.
  • the expanded volume is 10-30% greater than the volume of the bed "at rest”.
  • agitated states in the process of the present invention are fluidised and sub-fluidised regimes.
  • the bed may, in addition to the reaction gas which passes through the bed, be agitated by further means, such as stirrers.
  • the apparatus of the present invention is used for a process in which the bed of polymer particles is maintained in a tluidised state.
  • the reaction gas in such processes passes through the grid and acts as a fluidising gas, and comprises olefin reactants and usually other components such as hydrogen and inert compounds, such as nitrogen as known in the art.
  • the bed is maintained in a tluidised state by the fluidising gas "alone", by which is meant without mechanical stirring or other means to agitate the bed.
  • the reaction zone is preferably a vertically orientated reaction zone comprising a vertically orientated cylindrical section with a grid, known as a fluidisation grid, at its base and. above the vertically orientated cylindrical section, a section of expanded cross-section which acts as (and is usually referred to as) a disengagement zone.
  • the cylindrical section has a height H c as measured from the fluidisation grid to the top of the cylindrical section.
  • Reaction gas/fluidising gas is introduced into the reaction zone through the grid.
  • At or close to the top of the section of expanded cross-section is located the outlet for removal of the fluidising gas from the reaction zone.
  • Such reaction zones comprising a cylindrical "reactor" and a disengagement zone with an enlarged diameter are well-known in the art.
  • one or more inlets for introduction of recycled solids to the reaction zone may be provided.
  • the one or more inlets for introduction of recycled solids to the reaction zone are preferably located at a height of between 0 and 0.5 x H c above the fluidisation grid.
  • the inlets are located at a height of more than 0.01 x H c
  • the solids separation unit in the apparatus according to the present invention may be any device for separating solids present in the reaction gas stream exiting the reaction zone. Examples include an elbow concentrator device (e.g. pipe diverter). a filter or a cyclone.
  • a cyclone is the preferred solids separation unit according to the present invention.
  • An example of a suitable cyclone is that described in EP 1487588.
  • the solids separation unit may consist of a single cyclone, or two or more cyclones, preferably in parallel. When multiple cyclones are used, each cyclone may optionally have its own dedicated feed line from the reactor.
  • the apparatus may also comprise a compressor.
  • the compressor can provide a motive gas to pass the separated solids, preferably continuously, from the solids outlet of the solids separation unit to the inlet for introduction of recycled solids to the reaction zone against the pressure therein.
  • the motive gas may be any suitable gas but is preferably a fraction of cooled recycle gas in the process.
  • the compressor is preferably located on a motive gas line upstream of where this is connected to the solids outlet of the solids separation unit.
  • the apparatus may also comprise an ejector located such that the separated solids may be passed to the reactor via said ejector, such as described in US 4,882,400 or US 2008 / 021 1 78.
  • the present invention also provides a process for the gas phase polymerisation of olefins, using an apparatus as described herein.
  • the present invention provides a process for the gas phase polymerisation of olefins in an apparatus according to either the first or the second aspect, and comprising:
  • the process of the third aspect of the present invention is preferably a tluidised bed polymerisation process.
  • the present invention will hereinafter be generally described with respect to the preferred process for the gas phase polymerisation of olefins using a tluidised bed, but the description may equally be applied to other agitated beds within the scope of the present invention.
  • the process of the third aspect of the present invention preferably has a polymer production rate of at least 40 tonnes/hour. More preferably the production rate is at least 50 tonnes/hour, such as at least 75 tonnes/hour. There is no particular upper limit to the production rate in the process of the present invention, although the production rate would typically be less than 100 tonnes/hour. In fact, the present invention is particularly applicable to larger scale plants since it is in such plants that the largest mounting structures would otherwise be required for the solids separation unit and also where the vibration issues with cyclones can otherwise be most significant.
  • the entrained solids such as at least 90% by weight, for example at least 98% by weight and even preferably 99% by weight of said solids are separated in the solids separation unit, e.g. in a cyclone.
  • the nature of these solids depends on many factors such as e.g. the catalyst and the polymerisation conditions.
  • the entrained solids are characterised by a particles size lower than 200 microns.
  • the separated sol ids are usually returned to the bed in the reaction /one.
  • the return of the separated solids can be done at one or several locations within the bed. In general, the use of one or two points of recycling is sufficient for operating reactor systems at production rates of 40 to 100 tonnes- hour.
  • the process is a "condensed mode" polymerisation process, where at least a portion of the total feed introduced to the reactor is provided in the form of a liquid which vaporises inside the reaction zone.
  • Condensed mode fluidised bed operation is described in, for example, EP 89691 , US 4,543,399, US 4,588,790, EP 696293, US
  • the process according to the present invention preferably comprises cooling at least a portion of the lluidising gas exiting the solids separation unit such that at least a portion of the gases are condensed to form a liquid, which liquid is introduced into the reaction zone.
  • the liquid introduced into the reaction zone vaporises within the reaction zone absorbing (and thereby "removing") heat generated by the exothermic polymerisation reaction.
  • the liquid may be introduced into the base of or the lower quarter of the reaction zone, preferably above the fluidisation grid.
  • the condensed mode operation may be characterised by the amount of liquid introduced into the reaction zone relative to the total gas flow exiting the reaction zone.
  • a level of condensation of 10wt% means that 10wt% of the total gas flow rate exiting the reaction zone is reinjected in liquid form.
  • the level of condensation is at least 10wt%. More preferably, the level of condensation is at least 2()wt%, such as in the range 20 to 50wt%.
  • the uncondensed gas and (condensed) liquid may be introduced into the fluidised bed in any suitable manner.
  • the mixture of uncondensed gas and liquid obtained from the cooling (condensation) step may be introduced into the reactor as a single stream.
  • the mixture of uncondensed gas and liquid may be split into one or more streams and introduced into the reactor at different points.
  • one or more gaseous portions of the stream may be separated and introduced to the reactor below the fluidisation grid, whilst one or more portions which include the liquid may be introduced above the fluidisation grid, preferably in the lower quarter of the fluidised bed.
  • At least 20 % by weight, preferably at least 40" o by weight of the total of the condensed liquids are reintroduced directly into the bed of polymer particles above the reactor grid.
  • Said liquid reintroduction is preferably made at a location which is less than 0.5 x H c . for example less than 0.4 x H c , or even less than 0.1 x H c ; also, said liquid can be reintroduced into the reactor at a height of more than 0.01 x H c .
  • the combination of this liquid reintroduction above the grid together with the recycling of the solids tines provides additional advantages in term of overall stability of operation of the polymerisation reactor.
  • the polymerisation process of the present invention is preferably a process for the polymerisation of ethylene or propylene (or a combination), preferably for the
  • Two or more polymerisable olefins may be present, in which case the olefin present in the highest amount by weight can generally be referred to as the principal olefin or monomer, and any other polymerisable olefins can be referred to as comonomers.
  • the comonomers when present, may be any olefin other than the principal olefin, typically having up to 10 carbon atoms.
  • ethylene may be a comonomer when propylene is the principal olefin and propylene may be a comonomer when ethylene is the principal olefin.
  • the one or more comonomers are selected from 1 -olefins having 4 to 10 carbon atoms, such as 1 -butene, 1 -hexene and 1 -octene.
  • 1 -olefins having 4 to 10 carbon atoms, such as 1 -butene, 1 -hexene and 1 -octene.
  • Usually, only a single comonomer is deliberately added to the process, although smaller amounts of other olefins may be formed as impurities e.g. via ethylene di- and
  • the principal olefin is ethylene, which is polymerised with a single 1 -olefin comonomer selected from 1 -butene, 1 -he ene and 1 -octene.
  • Any suitable catalyst may be used in the process of the present invention.
  • suitable catalysts include chromium-type (or "Phillips") catalysts, Ziegler-type catalysts, late transition metal catalysts and metallocene-type catalysts.
  • the present invention is particularly applicable to single site metal locene-type catalysts and Ziegler catalysts.
  • single site metal locene catalysts these have a relatively high activity and ability to incorporate "heavier" co-monomers into the polyolefin formed (by which is meant comonomers having a larger molecular weight than the principal olefin) meaning that relatively low concentrations of such comonomers are required in the gas phase to give the desired comonomer content in the resultant polymer.
  • Figure 1 shows a fluidised bed polymerisation apparatus according to the present inv ention.
  • an apparatus comprising a v ertically orientated reaction zone comprising a vertically orientated cylindrical section ( 1 ) with a fluidisation grid (2) defining its base, and with a disengagement zone (3 ), being an area of expanded cross-section compared to the cylindrical section, connected to the top of the cylindrical section.
  • Said cylindrical section ( 1 ) has a height H L from the fluidisation grid to the top of the cylindrical section,
  • An outlet (4) for removal of reaction gas from the reaction zone is provided at the top of the disengagement zone (3).
  • the apparatus also comprises a cyclone (5) provided with an inlet (6) fluidly connected to the outlet (4) for removal of the reaction gas from the reaction zone via pipework (7).
  • the inlet of the cyclone (6)(solids separation unit) is located at a vertical height lower than the outlet (4) for removal of reaction gas from the reaction zone, and the pipework comprises three sections: -
  • a dotted line which represents a nominal straight line drawn between the inlet of the cyclone (6) and the outlet (4) for removal of reaction gas from the reaction zone. This makes an angle to the horizontal with an overall downwards direction compared to the horizontal in the direction from the outlet (4) for removal of reaction gas from the reaction zone to the inlet (6) of the cyclone.
  • FIG. 1 Further shown in Figure 1 is a gas removal line (8), by which reaction gas freed of entrained solids is passed to a cooling stage (9), and from which is recovered a cooled recycle stream which is passed via line ( 10) and compressor ( 1 1 ) and back to the reaction zone. It will be apparent to the person skilled in the art that variations on this configuration are possible. For example, it is possible to compress the gas removed from the reactor prior to cool ing.
  • the separated solids are recovered from the cyclone (5) via line ( 12) and subsequently to an inlet ( 13) for introduction of recycled solids into the lower half of the reaction zone ( 1 ).
  • a fraction of cooled recycle gas in the process is passed via compressor (14) and used as a motive gas to assist in this introduction.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Polymerisation Methods In General (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un appareil et un procédé pour la polymérisation en phase gazeuse d'oléfines, l'appareil comprenant : a) une zone de réaction comprenant une grille à sa base, b) une entrée située dans la moitié inférieure de la zone de réaction pour l'introduction d'un gaz de réaction dans la zone de réaction, c) une sortie située dans la moitié supérieure de la zone de réaction pour le retrait du gaz de réaction de la zone de réaction, et d) une unité de séparation des solides comportant une entrée connectée en relation fluidique à la sortie pour l'évacuation du gaz de réaction de la zone de réaction, caractérisé en ce que l'entrée de l'unité de séparation des solides est située à une hauteur verticale plus basse que la sortie pour l'évacuation du gaz de réaction de la zone de réaction, et tel que l'angle avec l'horizontal d'une ligne droite tracée entre l'entrée de l'unité de séparation des solides et la sortie pour le retrait du gaz de réaction de la zone de réaction est supérieur à 20°.
PCT/EP2011/071299 2010-11-29 2011-11-29 Appareil et procédé pour la polymérisation d'oléfines WO2012072639A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201180057160.4A CN103221124B (zh) 2010-11-29 2011-11-29 烯烃聚合用设备和方法
EP11788493.2A EP2646139B1 (fr) 2010-11-29 2011-11-29 Appareil et procédé pour la polymérisation d'oléfines
US13/885,574 US8765885B2 (en) 2010-11-29 2011-11-29 Apparatus and process for the polymerisation of olefins

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10192943.8 2010-11-29
EP10192943A EP2457647A1 (fr) 2010-11-29 2010-11-29 Appareil et procédé

Publications (1)

Publication Number Publication Date
WO2012072639A1 true WO2012072639A1 (fr) 2012-06-07

Family

ID=43827594

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/071299 WO2012072639A1 (fr) 2010-11-29 2011-11-29 Appareil et procédé pour la polymérisation d'oléfines

Country Status (4)

Country Link
US (1) US8765885B2 (fr)
EP (2) EP2457647A1 (fr)
CN (1) CN103221124B (fr)
WO (1) WO2012072639A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028172B (zh) * 2014-06-27 2018-05-25 英尼奥斯欧洲股份公司 用于氨氧化反应器的氨进料的控制
EP3418308B1 (fr) 2017-06-20 2020-03-11 Borealis AG Procédé, système et utilisation d'un agencement pour la polymérisation d'oléfines
CN111718437A (zh) * 2020-06-11 2020-09-29 国家能源集团宁夏煤业有限责任公司 共聚反应系统和制备抗冲聚丙烯的方法

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1413613A (en) 1972-11-17 1975-11-12 Naphtachimie Sa Process for the dry polymerisation of olefins
EP0089691A2 (fr) 1982-03-24 1983-09-28 Union Carbide Corporation Procédé continu de préparation d'un polymère dans un réacteur à lit fluidisé
JPS59176305A (ja) * 1983-03-28 1984-10-05 Mitsui Petrochem Ind Ltd 気相重合方法
US4543399A (en) 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
US4640963A (en) 1985-02-15 1987-02-03 Standard Oil Company (Indiana) Method and apparatus for recycle of entrained solids in off-gas from a gas-phase polyolefin reactor
US4882400A (en) 1987-07-31 1989-11-21 Bp Chemicals Limited Process for gas phase polymerization of olefins in a fluidized bed reactor
US5382638A (en) 1989-01-31 1995-01-17 Bp Chemicals Limited Apparatus for gas phase polymerization of olefins in a fluidized bed reactor
US5405922A (en) 1993-04-26 1995-04-11 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
EP0696293A1 (fr) 1993-04-26 1996-02-14 Exxon Chemical Patents Inc. Procede de polymerisation de monomeres dans des lits fluidifies
EP0699213A1 (fr) 1993-05-20 1996-03-06 BP Chemicals Limited Procede de polymerisation
US20010018500A1 (en) * 2000-01-18 2001-08-30 Solvay Polyolefins Europe-Belgium (Societe Anonyme) Process for manufacturing olefin polymers
EP1487588A1 (fr) 2002-03-19 2004-12-22 BP Chemicals Limited Separation de gaz et de solides au moyen d'un cyclone
WO2006050919A1 (fr) * 2004-11-11 2006-05-18 Basell Polyolefine Gmbh Appareil pour la polymérisation d'oléfines, en particulier de l'éthylène, en phase gazeuse
US20080021178A1 (en) 2006-07-20 2008-01-24 Matthew Howard Scott Process and apparatus for olefin polymerization in a fluidized bed reactor
WO2010049619A1 (fr) * 2008-10-30 2010-05-06 Jean-Xavier Morin Dispositif de lit fluidise a fluidisation rapide et a flux sature de solides circulants

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3002963A (en) * 1957-04-22 1961-10-03 Phillips Petroleum Co Gas phase polymerization utilizing a free-settling, fluidized catalyst and reactor system therefor

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1413613A (en) 1972-11-17 1975-11-12 Naphtachimie Sa Process for the dry polymerisation of olefins
EP0089691A2 (fr) 1982-03-24 1983-09-28 Union Carbide Corporation Procédé continu de préparation d'un polymère dans un réacteur à lit fluidisé
US4543399A (en) 1982-03-24 1985-09-24 Union Carbide Corporation Fluidized bed reaction systems
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
JPS59176305A (ja) * 1983-03-28 1984-10-05 Mitsui Petrochem Ind Ltd 気相重合方法
US4640963A (en) 1985-02-15 1987-02-03 Standard Oil Company (Indiana) Method and apparatus for recycle of entrained solids in off-gas from a gas-phase polyolefin reactor
US4882400A (en) 1987-07-31 1989-11-21 Bp Chemicals Limited Process for gas phase polymerization of olefins in a fluidized bed reactor
US5382638A (en) 1989-01-31 1995-01-17 Bp Chemicals Limited Apparatus for gas phase polymerization of olefins in a fluidized bed reactor
US5405922A (en) 1993-04-26 1995-04-11 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
EP0696293A1 (fr) 1993-04-26 1996-02-14 Exxon Chemical Patents Inc. Procede de polymerisation de monomeres dans des lits fluidifies
EP0699213A1 (fr) 1993-05-20 1996-03-06 BP Chemicals Limited Procede de polymerisation
US5541270A (en) 1993-05-20 1996-07-30 Bp Chemicals Limited Polymerization process
US20010018500A1 (en) * 2000-01-18 2001-08-30 Solvay Polyolefins Europe-Belgium (Societe Anonyme) Process for manufacturing olefin polymers
EP1487588A1 (fr) 2002-03-19 2004-12-22 BP Chemicals Limited Separation de gaz et de solides au moyen d'un cyclone
WO2006050919A1 (fr) * 2004-11-11 2006-05-18 Basell Polyolefine Gmbh Appareil pour la polymérisation d'oléfines, en particulier de l'éthylène, en phase gazeuse
US20080021178A1 (en) 2006-07-20 2008-01-24 Matthew Howard Scott Process and apparatus for olefin polymerization in a fluidized bed reactor
WO2010049619A1 (fr) * 2008-10-30 2010-05-06 Jean-Xavier Morin Dispositif de lit fluidise a fluidisation rapide et a flux sature de solides circulants

Also Published As

Publication number Publication date
US8765885B2 (en) 2014-07-01
CN103221124A (zh) 2013-07-24
EP2646139A1 (fr) 2013-10-09
EP2457647A1 (fr) 2012-05-30
EP2646139B1 (fr) 2017-11-15
CN103221124B (zh) 2015-11-25
US20130331535A1 (en) 2013-12-12

Similar Documents

Publication Publication Date Title
EP1962996B1 (fr) Procede en phase gazeuse et dispositif pour la polymerisation d'olefines
CN105873958B (zh) 用于在流化床中聚合烯烃的方法
US8686097B2 (en) System and method for processing reactor polymerization effluent
RU2610541C2 (ru) Способ дегазации и придания промежуточных свойств частичкам полиолефина, полученным при полимеризации олефинов
US11220558B2 (en) Method, an arrangement and use of an arrangement of preparing polymer
EP1613668B1 (fr) Procede de polymerisation d'olefine en phase gazeuse
EP2723781A1 (fr) Procédé et appareil pour décharger un polymère d'un réacteur en phase gazeuse
EP1183097A1 (fr) Procede et appareil de polymerisation d'olefine en phase gazeuse
EP2646139B1 (fr) Appareil et procédé pour la polymérisation d'oléfines
KR101530752B1 (ko) 가스상 유동층 중합 반응을 위한 장치 및 방법
EP2528953B1 (fr) Procédé de polymérisation d'oléfines en phase gazeuse
CN112135845B (en) Process for polymerizing olefins in a gas phase reactor with improved thermal homogeneity

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11788493

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
REEP Request for entry into the european phase

Ref document number: 2011788493

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011788493

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 13885574

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE